US11597788B2 - Light curable composition - Google Patents
Light curable composition Download PDFInfo
- Publication number
- US11597788B2 US11597788B2 US17/225,864 US202117225864A US11597788B2 US 11597788 B2 US11597788 B2 US 11597788B2 US 202117225864 A US202117225864 A US 202117225864A US 11597788 B2 US11597788 B2 US 11597788B2
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- US
- United States
- Prior art keywords
- curable composition
- light curable
- acrylate
- meth
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 68
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 44
- -1 acrylamide compound Chemical class 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 2
- SVNDCMCAPDWHPV-UHFFFAOYSA-N 2-[2-(1,3-benzoxazol-2-yl)-1,2-diphenylethenyl]-1,3-benzoxazole Chemical class C1=CC=CC=C1C(C=1OC2=CC=CC=C2N=1)=C(C=1C=CC=CC=1)C1=NC2=CC=CC=C2O1 SVNDCMCAPDWHPV-UHFFFAOYSA-N 0.000 claims description 2
- PHBSPYGHSRVOHY-UHFFFAOYSA-N 2-[2-(1,3-benzoxazol-2-yl)thiophen-3-yl]-1,3-benzoxazole Chemical class C1=CC=C2OC(C3=C(C=4OC5=CC=CC=C5N=4)C=CS3)=NC2=C1 PHBSPYGHSRVOHY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010146 3D printing Methods 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 description 12
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 5
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 3
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- AIXZBGVLNVRQSS-UHFFFAOYSA-N 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound CC(C)(C)C1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=C(C=C4N=3)C(C)(C)C)=NC2=C1 AIXZBGVLNVRQSS-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- PSGCQDPCAWOCSH-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C=C)C[C@@H]1C2(C)C PSGCQDPCAWOCSH-BREBYQMCSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 2
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 2
- YNXCGLKMOXLBOD-UHFFFAOYSA-N oxolan-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCCO1 YNXCGLKMOXLBOD-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- XPEMPJFPRCHICU-UHFFFAOYSA-N (1-tert-butylcyclohexyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C(C)(C)C)CCCCC1 XPEMPJFPRCHICU-UHFFFAOYSA-N 0.000 description 1
- QRWAIZJYJNLOPG-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) acetate Chemical compound C=1C=CC=CC=1C(OC(=O)C)C(=O)C1=CC=CC=C1 QRWAIZJYJNLOPG-UHFFFAOYSA-N 0.000 description 1
- YFKBXYGUSOXJGS-UHFFFAOYSA-N 1,3-Diphenyl-2-propanone Chemical compound C=1C=CC=CC=1CC(=O)CC1=CC=CC=C1 YFKBXYGUSOXJGS-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- YMZIFDLWYUSZCC-UHFFFAOYSA-N 2,6-dibromo-4-nitroaniline Chemical compound NC1=C(Br)C=C([N+]([O-])=O)C=C1Br YMZIFDLWYUSZCC-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- DABQKEQFLJIRHU-UHFFFAOYSA-N 2-Propenoic acid, 2-methyl-, 3,3,5-trimethylcyclohexyl ester Chemical compound CC1CC(OC(=O)C(C)=C)CC(C)(C)C1 DABQKEQFLJIRHU-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- ILZXXGLGJZQLTR-UHFFFAOYSA-N 2-phenylethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=CC=C1 ILZXXGLGJZQLTR-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- HPSGLFKWHYAKSF-UHFFFAOYSA-N 2-phenylethyl prop-2-enoate Chemical compound C=CC(=O)OCCC1=CC=CC=C1 HPSGLFKWHYAKSF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- RFMQOHXWHFHOJF-UHFFFAOYSA-N cyano thiocyanate Chemical compound N#CSC#N RFMQOHXWHFHOJF-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- GGMYKFODAVNSDF-UHFFFAOYSA-N o-phenyl phenylsulfanylmethanethioate Chemical compound C=1C=CC=CC=1SC(=S)OC1=CC=CC=C1 GGMYKFODAVNSDF-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YYWLHHUMIIIZDH-UHFFFAOYSA-N s-benzoylsulfanyl benzenecarbothioate Chemical class C=1C=CC=CC=1C(=O)SSC(=O)C1=CC=CC=C1 YYWLHHUMIIIZDH-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
Definitions
- This invention relates to a light curable composition, comprising at least one (meth)acrylate monomer, at least one acrylamide compound, at least one (meth)acrylate oligomer, and at least one photoinitiator.
- the light curable composition of the present invention exhibits excellent elongation property after curing and is suitable to be applied for 3D printing.
- Three-dimensional (3D) printing processes such as Stereolithography (SLA) and Digital Light Processing (DLP), are based on the layer-wise polymerization of Ultraviolet (UV) sensitive resins.
- UV sensitive resins widely used for the 3D printing processes.
- Traditional (meth)acrylic based resins are rigid and have poor elongation property after curing.
- the products of the traditional (meth)acrylic based resins are fragile, and the application of the products are therefore limited.
- the present invention relates to a light curable composition, comprising:
- the light curable composition of the invention exhibits excellent elongation property after curing and is suitable to be applied for 3D printing.
- the present invention also relates to a cured product of the light curable composition.
- the cured product of the present invention may be in a form of a 3D article formed from the light curable composition printed by a 3D printer.
- the present invention also relates to an article bonded by light curable composition.
- (meth)acrylate refers to both or any one of “acrylate” and “methacrylate”.
- (meth)acrylic refers to both or any one of “acrylic” and “methacrylic”.
- the term “monomer” refers to a polymer building block which has a defined molecular structure and which can be reacted to form a part of a polymer.
- oligomer refers to a molecule that comprises at least two repeat units.
- hydrocarbon group refers to an organic compound consisting of carbon and hydrogen.
- Example of hydrocarbon group includes but limited to an alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, tertiary butyl, isobutyl and the groups alike; an o alkenyl group, such as vinyl, allyl, butenyl, pentenyl, hexenyl and the groups alike; an aralkyl group, such as benzyl, phenethyl, 2-(2,4,6-trimethylphenyl)propyl and the groups alike; or an aryl group, such as phenyl, tolyl, xyxyl and the groups alike.
- alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, tertiary butyl, isobutyl and
- optionally substituted in the term of “optionally substituted hydrocarbon group” means that one or more hydrogens on the hydrocarbon group may be replaced with a corresponding number of substituents preferably selected from halogen, nitro, azido, amino, carbonyl, ester, cyano, sulfide, sulfate, sulfoxide, sulfone, sulfone groups, and the likes.
- glass transition temperature refers to a temperature at which a polymer transitions between a highly elastic state and a glassy state. Glass transition temperature may be measured, for example, by differential scanning calorimetry (DSC).
- DSC differential scanning calorimetry
- the light curable composition of the present invention comprises at least one (meth)acrylate monomer.
- the (meth)acrylate monomer refers to any common (meth)acrylate monomer capable of polymerization, and having at least one group represented by the following general formula:
- R is a hydrogen or a methyl group.
- Illustrative (meth)acrylate monomers include isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA), tetrahydrofurfuryl acrylate (THFA), (5-ethyl-1,3-dioxan-5-YI)methyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, t-butylcyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate, dicyclopentanyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethyl
- the (meth)acrylate monomer has a glass transition temperature from ⁇ 60 to 120° C., preferably from ⁇ 20 to 120° C., more preferably from 25 to 120° C., and even more preferably from 80 to 100° C. it is surprisingly found that when incorporating (meth)acrylate monomer with proper glass transition temperature, the elongation property of the cured product of the light curable composition can be improved.
- Examples of commercially available (meth)acrylate monomers are, for example, SR531, SR508 and SR285 from Sartomer.
- the amount of the (meth)acrylate monomer is preferably from 10 to 90%, and more preferably from 40 to 60% by weight based on the total weight of the light curable composition.
- the light curable composition of the present invention comprises at least one acrylamide compound.
- the acrylamide compound refers to a compound having at least one group represented by CH 2 ⁇ CR 4 —CO—N in each molecule, wherein R 4 is a hydrogen or a methyl group.
- Illustrative acrylamide compounds include 4-acryloylmorpholine (ACMO), N,N-dimethylacrylamide (DMAA), N,N-Diethyl-2-propenamide (DEAA), and N-hydroxyethylacrylamide (HEAA).
- the acrylamide compound can be used alone or in combination.
- the light curable composition preferably comprises at least one acrylamide compound having the amide nitrogen as a member of a cyclic group.
- the cyclic group may be aromatic heterocyclic groups having 4 to 20 atoms in the cyclic group; and saturated and unsaturated aliphatic heterocyclic groups having 4 to 20 atoms in the cyclic group.
- the cyclic group may contain additional hetero atoms such as N, O, S, P, and Si other than the amide nitrogen atom.
- the cyclic group may be optionally substituted with by groups selected from alkyl groups of 1 to 6 carbon atoms, hydroxyl, acyloxy, alkoxy of 1 to 6 carbon atoms, cyano, halo, phenyl, and benzo groups.
- the light curable composition comprises at least one acrylamide compound having the amide nitrogen as a member of a saturated and unsaturated aliphatic heterocyclic group having 4 to 20 atoms in the cyclic group.
- the light curable composition comprises at least one acrylamide compound having a structure represented by the general formula (1). It is surprisingly found that when incorporating acrylamide compound having a structure represented by the general formula (1), the elongation property of the cured product of the light curable composition can be further improved.
- R 1 is a hydrogen or a methyl group
- R 2 and R 3 are each independently an optionally substituted divalent hydrocarbon group.
- R 2 and R 3 are each independently a C 1 to C 10 optionally substituted divalent hydrocarbon group.
- the divalent hydrocarbon group include but not limited to a methylene group, ethylene group, and trimethylene group.
- Examples of commercially available acrylamide compound are ACMOTM, DMAATM and DEAATM from KJ Chemicals corporation.
- the amount of the acrylamide compound is preferably from 5% to 80%, and more preferably from 10 to 70% by weight based on the total weight of the light curable composition.
- the light curable composition of the present invention comprises at least one (meth)acrylate oligomer.
- the (meth)acrylate oligomer refers to an oligomer having at least one acryloyl group or at least one methacrylol group per molecule.
- the (meth)acrylate oligomer has two acryloyl groups or two methacrylol groups per molecule.
- Illustrative (meth)acrylate oligomer includes a polyurethane (meth)acrylate oligomer, a polyisoprene (meth)acrylate oligomer, a polybutadiene (meth)acrylate oligomer, a polyester (meth)acrylate oligomer and a polyether (meth)acrylate oligomer.
- the (meth)acrylate oligomer can be used alone or in combination.
- polyurethane (meth)acrylate oligomer is used in the light curable composition of the present invention.
- the (meth)acrylate oligomer has a glass transition temperature from ⁇ 80 to 60° C., preferably from ⁇ 60 to 20° C., more preferably from ⁇ 60 to 0° C., and even more preferably from ⁇ 60 to ⁇ 10° C. It is surprisingly found that when incorporating (meth)acrylate oligomer having a low glass transition temperature, the elongation property of the cured product of the light curable composition can be further improved.
- Examples of commercially available (meth)acrylate oligomers are, for example, BR-3641AJ, BR-3741AJ, BR-3641AA, BR-345, BRC-443, BRC-443D, BRC-843, BRC-843S, BRC-843D, BR7432 GB, BR-641D, BR-641S, BR-744BT, and BR-744SD from Dymax Oligomers & Coatings; CN8881NS, CN8882NS, CN8883NS, CN8884NS, CN8888NS, and CN9014NS from Sartomer; and EBECRYL-230, EBECRYL-231, EBECRYL-242, EBECRYL-244, EBECRYL-246, EBECRYL-4491, EBECRYL-4483, T EBECRYL-8841, EBECRYL-8804, and EBECRYL-6603 from AlInex Group Companies.
- the amount of the (meth)acrylate oligomer is preferably from 10% to 90%, and more preferably from 20% to 60% by weight based on the total weight of the light curable composition.
- the light curable composition of the present invention comprises at least one photoinitiator.
- the photoinitiator refers to any common photoinitiator and is preferably to include at least one free radical photoinitiator, for example selected from benzophenone, acetophenone, chlorinated acetophenone, dialkoxyacetophenones, dialkylhydroxyacetophenones, dialkylhydroxyacetophenone esters, benzoin acetate, benzoin, benzoin alkyl ethers, dimethoxybenzion, dibenzylketone, benzoylcyclohexanol and other aromatic ketones, acyloxime esters, acylphosphophine oxides, acylphosphosphonates, ketosulfides, dibenzoyldisulphides, diphenyldithiocarbonate, and dipheyl(2,4,6-trimethylbenzoyl) phosphine oxide.
- the photoinitiator can be used alone or in any combination.
- Examples of commercially available photoinitiators include but not limited to Irgacure 184, Irgacure 500, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 1700, Irgacure 651, Irgacure 819, Irgacure 1000, Irgacure 1300, Irgacure 1870, Darocur 1173, Darocur 2959, Darocur 4265 and Darocur TPO, from Ciba Specialty Chemicals; Lucerin TPO, from BASF AG; Esacure KT046, Esacure KIP150, EsacureKT37 and Esacure EDB, from LAMBERTI; H-Nu 470 and H-Nu 470X, from SPECTRA GROUP Ltd.; and Genopol TX-1, from Rahn AG.
- the amount of the photoinitiator of the invention is from 0.1% to 8%, preferably from 1% to 5%, and more preferably from 3% to 5% by weight based on the total weight of the light curable composition.
- the light curable composition may optionally include at least one fluorescent brightener.
- the fluorescent brightener includes but not limited to benzoxazole derivatives, bis-benzoxazoles; bis-benzoxazolyl-stilbenes; bis-benzoxazolyl-thiophenes, thiophenediyl benzoxazoles, 2,5-thiophenediylbis-(5-tert-butyl-1,3-benzoxazoles).
- the fluorescent brightener can be used alone or in combination.
- fluorescent brighteners examples include but not limited to Tinopal OB and Uvitex OB, from BASF.
- the amount of the fluorescent brightener of the invention is from 0% to 2%, preferably from 0.05 to 1%, and more preferably from 0.05% to 0.5% by weight based on the total weight of the light curable composition.
- the light curable composition comprises:
- the light curable composition of the present invention may be prepared by mixing all the components together by any common method and apparatus known in the art.
- the light curable composition of the present invention may be cured by actinic ray that has sufficient energy to initiate a polymerization or cross-linking reaction.
- the actinic ray includes but is not limited to ⁇ -rays, ⁇ -rays, ultraviolet radiation (UV), visible light, and electron beams.
- UV radiation and electron beams are used for the curing of light curable composition.
- UV radiation is chosen as the source of energy for the curing of light curable composition.
- the light curable composition can be cured by UV LED at a wavelength of 405 nm and with an energy of 10-100 mw/cm 2 for 1 to 20 seconds.
- Representative examples of the UV light source include LED UV cure equipment (model 97070, from Loctite Henkel), and Fusion UV equipment (LH6BPS, from Fusion UV System Inc.).
- the light curable composition of the present invention may be printed to form a 3D article by the following steps:
- the light curable composition of the present invention may be printed using a 3D printer, such as Ember from Autodesk; Form 1+ from Formlabs; PR 10 from Henkel; and Lite 100 from Union tech.
- a 3D printer such as Ember from Autodesk; Form 1+ from Formlabs; PR 10 from Henkel; and Lite 100 from Union tech.
- the elongation property of the 3D article cured from the light curable composition of the present invention may be assessed according to ASTM638-14.
- the 3D article cured from the light curable composition of the present invention preferably has an elongation at break greater than or equal to 100%, more preferably greater than or equal to 120%, and even more preferably greater than or equal to 140%.
- the light curable composition was printed to form a 3D article using an Ember printer from Autodesk, by the following steps:
- the elongation property of the 3D article formed by the light curable composition was measured according to ASTM D638-14 using Instron Universal test machine at a test speed of 100 mm/min.
- a light curable composition was prepared, according to Table 1, by mixing the components selected from:
- the glass transition temperature of the (meth)acrylate monomer and (meth)acrylate oligomer also played a key role for the elongation property of 3D article formed from the light curable composition.
- Example 2, 5, and 6 when incorporating a (meth)acrylate monomer with high glass transition temperature in the light curable composition, the 3D article had better elongation at break.
- Example 2, 7, and 8 when incorporating a (meth)acrylate oligomer with low glass transition temperature in the light curable composition, the 3D article had better elongation at break.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
-
- (a) at least one (meth)acrylate monomer;
- (b) at least one acrylamide compound;
- (c) at least one (meth)acrylate oligomer; and
- (d) at least one photoinitiator.
- a) a digital model of a 3D article to be printed is provided;
- b) the digital model of the 3D article is sliced into a number of horizontal planes, and each of the horizontal plane is converted into a two-dimensional image;
- c) a layer of the light curable composition is deposited on a surface of the building platform;
- d) one two-dimensional image is projected with aid of the actinic ray onto the layer of the light curable composition for curing;
- e) another layer of the light curable composition is deposited onto the cured layer of the light curable composition in the previous step; and
- f) steps of d) and e) are repeated to form the 3D article.
- a) a digital model of a 3D article to be printed was provided according to the type V specimen in ASTM638-14;
- b) the digital model of the 3D article was sliced into 64 horizontal planes with a height of 0.05 mm for each horizontal plane, and each of the horizontal plane was converted into a two-dimensional image by Autodesk Print Studio software;
- c) a first layer of the light curable composition was deposited on a surface of the building platform and was left stand for 5 seconds before being exposed to UV radiation;
- d) a first two-dimensional image was projected with aid of the UV radiation at a wavelength of 405 nm and with an energy of 20 mw/cm2 onto the first layer of the light curable composition, and the first layer of the light curable composition was exposed under the UV radiation for 8 seconds;
- e) a second layer of the light curable composition was deposited onto the cured first layer and was left stand for 5 seconds before being exposed to UV radiation;
- f) a second two-dimensional image was projected with aid of the UV radiation at a wavelength of 405 nm and with an energy of 20 mw/cm2 onto the second layer of the light curable composition, and the second layer of the light curable composition was exposed under the UV radiation for 4 seconds;
- g) a third layer of the light curable composition was deposited onto the cured second layer and was left stand for 1.5 seconds before being exposed to UV radiation;
- h) a third two-dimensional image was projected with aid of the UV radiation at a wavelength of 405 nm and with an energy of 20 mw/cm2 onto the third layer of the light curable composition, and the third layer of the light curable composition was exposed under the UV radiation for 2.2 seconds;
- i) steps g) and h) were repeated for the rest of layers to form the 3D article.
- ACMO (Acryloyl morpholine, available from KJ Chemicals Corporation);
- DMAA (N,N-Dimethyl acrylamide, available from KJ Chemicals Corporation);
- DEAA (N,N-Diethyl acrylamide, available from KJ Chemicals Corporation);
- TPO (2,4,6-Trimethylbenzoyl diphenyl phosphine oxide, Chivacure TPO, available from Chitec Chemical);
- Tinopal OB CO (2, 5-thiophenediylbis (5-tert-butyl-1, 3-benzoxazole), available from BASF);
- Ebecryl 230 (Aliphatic Urethane Diacrylate, available from AlInex Group Companies, Tg=−55° C.);
- BRC 843S (Hydrophobic Urethane Acrylates, available from Dymax Oligomers & Coatings, Tg=−9° C.);
- BRC 443D (Hydrophobic Urethane Acrylates, available from Dymax Oligomers & Coatings, Tg=41° C.);
- SR 531 (5-Ethyl-1,3-Dioxan-5-YI)Methyl Acrylate, available from Sartomer, Tg=32° C.);
- ISTA ((Isostearyl acrylate, NK ESTER S-1800ALC available from Shin-Nakamura Chemical Co., Ltd., Tg=−18° C.);
- SR 285 (Tetrahydrofurfuryl acrylate, available from Sartomer, Tg=−15° C.); and
- SR 506 (Isobornyl acrylate, available from Sartomer, Tg=88° C.).
TABLE 1 |
Light curable composition |
Weight % |
Components | Ex. 1 | Ex. 2 | Ex. 3 | Ex. 4 | Ex. 5 | Ex. 6 | Ex. 7 | Ex. 8 | Ex. 9 |
ACMO | 19.4 | 19.4 | 19.4 | 19.4 | 19.4 | 19.4 | |||
DMAA | 19.4 | ||||||||
DEAA | 19.4 | ||||||||
TPO | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
Tinopal OBCO | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
Ebecryl 230 | 40 | 40 | 40 | 40 | 40 | 40 | 40 | ||
BRC 843S | 30 | ||||||||
BRC 443D | 30 | ||||||||
SR 531 | 20 | 40 | 40 | 40 | 50 | 50 | 39.4 | ||
ISTA | 20 | 20 | |||||||
SR 285 | 40 | ||||||||
SR 506 | 40 | ||||||||
TABLE 2 |
Elongation Property |
Ex. 1 | Ex. 2 | Ex. 3 | Ex. 4 | Ex. 5 | Ex. 6 | Ex. 7 | Ex.8 | Ex.9 | |
Elongation | 145 | 170 | 134.45 | 119.55 | 137.36 | 310.13 | 129.42 | 108.5 | 78 |
at break (%) | |||||||||
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CN113056496B (en) * | 2018-11-19 | 2023-09-08 | 应用材料公司 | Low viscosity UV curable formulation for 3D printing |
CN114181354B (en) * | 2021-12-20 | 2022-07-12 | 杭州之江有机硅化工有限公司 | UV (ultraviolet) photocuring composition with low moisture vapor transmission rate and preparation method thereof |
JP7187725B1 (en) | 2022-06-01 | 2022-12-12 | 第一工業製薬株式会社 | Curable composition and electric member |
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EP3864058A1 (en) | 2021-08-18 |
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CN112823171A (en) | 2021-05-18 |
EP3864058A4 (en) | 2022-07-20 |
US20210221930A1 (en) | 2021-07-22 |
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